U.S. patent application number 16/374119 was filed with the patent office on 2019-10-17 for liquid crystal composition and display using composition.
The applicant listed for this patent is Shijiazhuang Chengzhi Yonghua Display Material Co., Ltd. Invention is credited to Hongru GAO, Yapeng HUANG, Ruixiang LIANG, Junhong SU, Xuanfei SUN, Gang WEN, Wenxiao XING, Xiaoming XIONG.
Application Number | 20190316038 16/374119 |
Document ID | / |
Family ID | 68161452 |
Filed Date | 2019-10-17 |
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United States Patent
Application |
20190316038 |
Kind Code |
A1 |
LIANG; Ruixiang ; et
al. |
October 17, 2019 |
LIQUID CRYSTAL COMPOSITION AND DISPLAY USING COMPOSITION
Abstract
Provided are a polymerizable composition of a polymerizable
compound represented by formula I and a polymerizable compound
represented by formula II, a liquid crystal composition formed by
combining this polymerizable composition with a specific liquid
crystal component, particularly a PSVA liquid crystal composition
suitable for display or TV applications, and a PSA-IPS liquid
crystal composition for an IPS mode; in particular, the
polymerizable liquid crystal composition has a good solubility, and
an adjustable rate of polymerization and morphology after
polymerization; furthermore, a "material system" formed from the
selected polymerizable component and liquid crystal component has a
low rotary viscosity and good photoelectric properties, and has a
high VHR after (UV) photoradiation, this avoiding the problems of
the occurrence of afterimages in final displays, etc.
Inventors: |
LIANG; Ruixiang;
(Shijiazhuang, CN) ; XING; Wenxiao; (Shijiazhuang,
CN) ; WEN; Gang; (Shijiazhuang, CN) ; GAO;
Hongru; (Shijiazhuang, CN) ; SUN; Xuanfei;
(Shijiazhuang, CN) ; HUANG; Yapeng; (Shijiazhuang,
CN) ; XIONG; Xiaoming; (Shijiazhuang, CN) ;
SU; Junhong; (Shijiazhuang, CN) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Shijiazhuang Chengzhi Yonghua Display Material Co., Ltd |
Shijiazhuang |
|
CN |
|
|
Family ID: |
68161452 |
Appl. No.: |
16/374119 |
Filed: |
April 3, 2019 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C09K 19/3098 20130101;
C09K 19/3861 20130101; C09K 2019/3016 20130101; C09K 19/3491
20130101; C09K 2019/0448 20130101; C09K 2019/3009 20130101; C09K
2019/123 20130101; C09K 2019/3004 20130101; C09K 19/32 20130101;
C09K 19/3066 20130101; C09K 2019/3408 20130101; C09K 19/12
20130101; C09K 2019/3027 20130101; C09K 2019/122 20130101 |
International
Class: |
C09K 19/38 20060101
C09K019/38; C09K 19/12 20060101 C09K019/12; C09K 19/32 20060101
C09K019/32; C09K 19/30 20060101 C09K019/30 |
Foreign Application Data
Date |
Code |
Application Number |
Apr 13, 2018 |
CN |
201810329506.5 |
Claims
1. A polymerizable liquid crystal composition, comprising one or
more polymerizable liquid crystal compounds represented by formula
I and one or more polymerizable liquid crystal compounds
represented by formula II: ##STR00116## wherein ##STR00117## each
independently represent ##STR00118## each P independently
represents a polymerizable group ##STR00119## each Sp independently
represents a single bond, a C1-C5 alkyl group, a C2-C5 alkenyl
group, or a group formed by replacing any one or more unconnected
CH.sub.2 in a C1-C5 alkyl group or a C2-C5 alkenyl group by --O--,
--S--, --CO--, --CH.sub.2O--, --OCH.sub.2--, --COO--, --OOC-- or an
acrylate group; and n represents 0 or 1.
2. The polymerizable liquid crystal composition according to claim
1, wherein the compound represented by formula I is from compounds
represented by formulas I-1 to I-20, and the compound represented
by formula II is from compounds represented by formulas II-1 to
II-14 ##STR00120## ##STR00121## ##STR00122## ##STR00123##
##STR00124## wherein each S independently represents H, a C1-C5
alkyl group, a C1-C5 alkoxy group, a fluorine-substituted C1-C5
alkyl group, a fluorine-substituted C1-C5 alkoxy group, F or Cl,
wherein any one or more unconnected CH.sub.2 in the groups
represented by S may be independently replaced by --O--, --S--,
--CO--, --CH.sub.2O--, --OCH.sub.2--, --COO--, --OOC-- or an
acrylate group or a methacrylate group; each P independently
represents a polymerizable group ##STR00125## each Sp independently
represents a single bond, a C1-C5 alkyl group, a C2-C5 alkenyl
group, or a group formed by replacing any one or more unconnected
CH.sub.2 in a C1-C5 alkyl group or a C2-C5 alkenyl group by --O--,
--S--, --CO--, --CH.sub.2O--, --OCH.sub.2--, --COO--, --OOC-- or an
acrylate group; and each o independently represents 0, 1, 2 or
3.
3. The polymerizable liquid crystal composition according to claim
1, wherein the compound represented by formula I is from compounds
represented by formulas I-1-1 to I-20-19, and the compound
represented by formula II is from compounds represented by formulas
II-1-1 to II-15-13 ##STR00126## ##STR00127## ##STR00128##
##STR00129## ##STR00130## ##STR00131## ##STR00132## ##STR00133##
##STR00134## ##STR00135## ##STR00136## ##STR00137## ##STR00138##
##STR00139## ##STR00140## ##STR00141## ##STR00142## ##STR00143##
##STR00144## ##STR00145## ##STR00146## ##STR00147## ##STR00148##
##STR00149## ##STR00150## ##STR00151## ##STR00152## ##STR00153##
##STR00154## ##STR00155## ##STR00156## ##STR00157## ##STR00158##
##STR00159## ##STR00160## ##STR00161## ##STR00162## ##STR00163##
##STR00164## ##STR00165## ##STR00166## ##STR00167## ##STR00168##
##STR00169## ##STR00170## ##STR00171## ##STR00172## ##STR00173##
##STR00174## ##STR00175## ##STR00176## ##STR00177## ##STR00178##
##STR00179## ##STR00180## ##STR00181## ##STR00182## ##STR00183##
##STR00184## ##STR00185## ##STR00186## ##STR00187## ##STR00188##
##STR00189## ##STR00190## ##STR00191## ##STR00192##
##STR00193##
4. A liquid crystal composition, comprising the polymerizable
liquid crystal composition of claim 1 as a first component, one or
more compounds represented by formula IV as a second component, and
one or more compounds represented by formula V as a third
component, ##STR00194## wherein R.sub.1, R.sub.2, R.sub.3, and
R.sub.4 each independently represent an alkyl group having a carbon
atom number of 1-10, a fluorine-substituted alkyl group having a
carbon atom number of 1-10, an alkoxy group having a carbon atom
number of 1-10, a fluorine-substituted alkoxy group having a carbon
atom number of 1-10, an alkenyl group having a carbon atom number
of 2-10, a fluorine-substituted alkenyl group having a carbon atom
number of 2-10, an alkenoxy group having a carbon atom number of
3-8 or a fluorine-substituted alkenoxy group having a carbon atom
number of 3-8, wherein any one or more unconnected CH.sub.2 in the
groups represented by R.sub.3 and R.sub.4 may be substituted with
cyclopentyl, cyclobutyl or cyclopropyl; Z.sub.1 and Z.sub.2 each
independently represent a single bond, --CH.sub.2CH.sub.2-- or
--CH.sub.2O--; ##STR00195## each independently represent
##STR00196## each independently represent one or more of
##STR00197## m represents 1 or 2; and p represents 0, 1 or 2.
5. The liquid crystal composition according to claim 4, wherein in
said liquid crystal composition, the total mass content of the
polymerizable liquid crystal composition is 0.01%-1%, the total
mass content of said one or more compounds represented by formula
IV is 20%-80%, and the total mass content of said one or more
compounds represented by formula V is 20%-60%.
6. The liquid crystal composition according to claim 4, wherein
said one or more compounds represented by formula IV are one or
more compounds represented by formulas IV-1 to IV-15; and said one
or more compounds represented by formula V are one or more
compounds represented by formulas V-1 to V-12 ##STR00198##
##STR00199## ##STR00200## wherein R.sub.3 and R.sub.4 each
independently represent an alkyl group having a carbon atom number
of 1-10, a fluorine-substituted alkyl group having a carbon atom
number of 1-10, an alkoxy group having a carbon atom number of
1-10, a fluorine-substituted alkoxy group having a carbon atom
number of 1-10, an alkenyl group having a carbon atom number of
2-10, a fluorine-substituted alkenyl group having a carbon atom
number of 2-10, an alkenoxy group having a carbon atom number of
3-8 or a fluorine-substituted alkenoxy group having a carbon atom
number of 3-8, wherein any one or more unconnected CH.sub.2 in the
groups represented by R.sub.3 and R.sub.4 may be substituted with
cyclopentyl, cyclobutyl or cyclopropyl.
7. The liquid crystal composition according to claim 4, wherein
said liquid crystal composition is a negative liquid crystal
composition and further comprises one or more compounds represented
by formula VI: ##STR00201## wherein R.sub.5 and R.sub.6 each
independently represent an alkyl group having a carbon atom number
of 1-10, a fluorine-substituted alkyl group having a carbon atom
number of 1-10, an alkoxy group having a carbon atom number of
1-10, a fluorine-substituted alkoxy group having a carbon atom
number of 1-10, an alkenyl group having a carbon atom number of
2-10, a fluorine-substituted alkenyl group having a carbon atom
number of 2-10, an alkenoxy group having a carbon atom number of
3-8 or a fluorine-substituted alkenoxy group having a carbon atom
number of 3-8, wherein any one or more CH.sub.2 in the groups
represented by R.sub.5 and R.sub.6 may be replaced by cyclopentyl,
cyclobutyl or cyclopropyl; and W represents O, S or
--CH.sub.2O--.
8. The liquid crystal composition according to claim 4, further
comprising one or more compounds represented by formula VII
##STR00202## wherein R.sub.7 and R.sub.8 each independently
represent an alkyl group having a carbon atom number of 1-10, a
fluorine-substituted alkyl group having a carbon atom number of
1-10, an alkoxy group having a carbon atom number of 1-10, a
fluorine-substituted alkoxy group having a carbon atom number of
1-10, an alkenyl group having a carbon atom number of 2-10, a
fluorine-substituted alkenyl group having a carbon atom number of
2-10, an alkenoxy group having a carbon atom number of 3-8 or an
fluorine-substituted alkenoxy group having a carbon atom number of
3-8; and ##STR00203## each independently represent 1,4-phenylene,
1,4-cyclohexylene or 1,4-cyclohexenylene.
9. The liquid crystal composition according to claim 4, further
comprising at least one selected from compounds represented by
formula VII and/or IX, as a functional additive ##STR00204##
wherein R.sub.9 represents an alkyl group having a carbon atom
number of 1-10 or an alkoxy group having a carbon atom number of
1-10, and one or more methylene groups in the group represented by
R.sub.9 may be substituted with 1,4-cyclohexylene, 2,4-dioxane,
cyclopentyl and/or cyclopropyl; each Y independently represents H
or methyl; and X represents 8, 10 or 12.
10. A liquid crystal display element or liquid crystal display
comprising the liquid crystal composition of claim 4, wherein said
display element or display is an active matrix display element or
display or a passive matrix display element or display.
Description
TECHNICAL FIELD
[0001] The present invention relates to the liquid crystal display
field, and in particular relates to a liquid crystal composition
formed by combining a specific polymerizable liquid crystal
composition with a specific liquid crystal component, and a display
element or liquid crystal display comprising the liquid crystal
composition.
BACKGROUND ART
[0002] As the leader of flat panel displays, TFT-LCD has gradually
taken a dominant position in the display field. TFT-LCD is
currently mostly used in high-end fields where there are quite
strict requirements for viewing angle, e.g. aerospace, medicine,
and graphic image processing. However, when viewing a display at a
position deviated from the normal line perpendicular to the
display, the contrast of display pictures is significantly reduced,
and grayscale inversion even occurs when the viewing angle is
large, which may seriously affect the application field of TFT-LCD.
Therefore, from the birth of active matrix LCD, wide viewing angle
technologies have all the time been an important research topic for
liquid crystal display technicians[1].
[0003] At present, relatively popular wide viewing angle
technologies mainly include TN+Wide Film (TN+a wide viewing angle
polarizer); VA (vertical alignment wide viewing angle active matrix
display technologies), including PVA, MVA, PSVA, etc.; IPS
(in-plane switching display technology); FFS (fringe field
switching wide viewing technology), etc. Since vertical alignment
liquid crystal displays have excellent properties such as a higher
contrast and a fast response time, vertical alignment has become
the focus of current researches.
[0004] The liquid crystal vertical alignment (VA) technologies
realize the symmetry of optical properties by converting a
conventional single domain structure into a multi-domain structure,
and realize a wide viewing angle display by means of optical film
compensation. The advantage of the vertical alignment mode is that
the front contrast is extremely high and can easily reach a value
of 500:1 or more. VA mode LCDs operate in a normally black mode,
thereby greatly reducing the possibility of "bright spots" on LCD
panels. Polymerizable mesogenic units (RMs) are currently a very
popular and important topic in the display industry, and possible
application fields thereof include polymer stabilized alignment
(PSA) liquid crystal display, polymer stabilized blue-phase (PS-BP)
liquid crystal display, pattern retarder films, etc.
[0005] The PSA principle is being applied to different typical LC
displays such as PSA-VA, PSA-OCB, PS-IPS/FFS and PS-TN liquid
crystal displays. Taking the most widely used PSA-VA display as an
example, the pretilt angle of a liquid crystal cell can be obtained
by a PSA method, and the pretilt angle has a positive effect on the
response time. For PSA-VA displays, standard MVA or PVA pixel and
electrode designs can be used; however, if a specially patterned
design is used the electrode design on one side and no protrusion
design is used on the other end, the production can be
significantly simplified while the display is imparted with a very
good contrast and a very high light transmittance.
[0006] PSVA technology is a polymer-stabilized vertical alignment
technology jointly developed by AUO and Merck. This technology
mainly involves controlling the liquid crystal to tilt by TFT/ITO
electrodes with slits; in addition, photosensitive macromolecules
are added to the liquid crystal material, a panel is assembled, an
electric field is then applied to tilt the liquid crystal, a
photosensitive monomer in the liquid crystal is reacted by means of
ultraviolet light, and the liquid crystal is caused to have a
pretilt angle in accordance with the driving direction of the
electric field to achieve multi-domain characteristics[2].
Therefore, compared with MVA/PVA technology, the advantages of PSVA
are a good black state, a fast response time, a high transmittance,
low costs, etc.
[0007] It has been found in the prior art that LC mixtures and RMs
still have some disadvantages in applications in PSA displays.
First, so far not every desired soluble RM is suitable for use in
PSA displays; in addition, if it is desired to carry out a
polymerization by means of a UV light without the addition of a
photoinitiator (which may be advantageous for some applications),
the choice becomes narrower; furthermore, a "material system"
formed from an LC mixture (hereinafter also referred to as an "LC
host mixture") in combination with the selected polymerizable
component should have the lowest rotary viscosity and the best
photoelectric performance for increasing the "voltage holding
ratio" (VHR) to achieve effects. In terms of PSA-VA, a high VHR
after photoradiation using (UV) light is very important; otherwise,
the problems of the occurrence of afterimages in the display, etc.,
may be finally caused. So far, not all combinations of LC mixtures
and polymerizable components are suitable for PSA displays. This is
mainly due to the effects in the aspects of the UV-sensitive
wavelength of polymerizable units being too short, or there being
no or an insufficient tilt angle after light irradiation, or the
polymerizable component having a poorer homogeneity after light
irradiation, or due to the VHR after UV being lower for TFT display
applications, etc.
[0008] Due to the selection of different UV wavelengths and
irradiation processes by different device manufacturers,
corresponding polymers required for the optimal process are also
not the same, and it is very difficult to meet requirements of a
manufacturer by using a single polymer; to match up with different
manufacturers, the development of different polymerizable liquid
crystal compositions is the key to success, and different
polymerizable liquid crystal compositions may be formed by means of
the adjustment of different polymerizable liquid crystal compounds;
the polymerizable liquid crystal compositions formed by means of
adjustments as such may be adjusted for the rate of polymerization
according to the requirements of different manufacturers, and the
polymerizable component has a good effect on the rotary viscosity,
VHR and pretilt angle of the liquid crystal compounds; furthermore,
the composition has better solubility properties than a single
compound.
SUMMARY OF THE INVENTION
[0009] The present invention provides a polymerizable liquid
crystal composition, a liquid crystal composition formed by
combining such a polymerizable liquid crystal compound with a
specific liquid crystal component, a liquid crystal display element
or liquid crystal display comprising the liquid crystal
composition; in particular, a PSVA liquid crystal composition for
displays or TV applications, and a PSA-IPS liquid crystal
composition for an IPS mode; in particular, the polymerizable
liquid crystal composition has a good solubility and an adjustable
rate of polymerization; in addition, a "material system" formed
from the selected polymerizable liquid crystal composition and
liquid crystal component has a low rotary viscosity and good
photoelectric properties, and has a high VHR after (UV)
photoradiation, this avoiding the problems of the occurrence of
afterimages in final displays, etc.
[0010] In order to achieve the above-mentioned advantageous
technical effects, the present invention provides a polymerizable
liquid crystal composition characterized by comprising one or more
polymerizable liquid crystal compounds represented by formula I and
one or more polymerizable liquid crystal compounds represented by
formula II:
##STR00001##
[0011] wherein
##STR00002##
each independently represent
##STR00003##
[0012] each P independently represents a polymerizable group
##STR00004##
[0013] each Sp independently represents a single bond, a C1-C5
alkyl group, a C2-C5 alkenyl group, or a group formed by replacing
any one or more unconnected CH.sub.2 in a C1-C5 alkyl group or a
C2-C5 alkenyl group by --O--, --S--, --CO--, --CH.sub.2O--,
--OCH.sub.2--, --COO--, --OOC-- or an acrylate group; and
[0014] n represents 0 or 1.
[0015] The present invention further provides a liquid crystal
composition comprising the polymerizable liquid crystal composition
of the present invention as a first component, one or more
compounds represented by formula IV as a second component and one
or more compounds represented by formula V as a third
component:
##STR00005##
[0016] wherein
[0017] R.sub.1, R.sub.2, R.sub.3, and R.sub.4 each independently
represent an alkyl group having a carbon atom number of 1-10, a
fluorine-substituted alkyl group having a carbon atom number of
1-10, an alkoxy group having a carbon atom number of 1-10, a
fluorine-substituted alkoxy group having a carbon atom number of
1-10, an alkenyl group having a carbon atom number of 2-10, a
fluorine-substituted alkenyl group having a carbon atom number of
2-10, an alkenoxy group having a carbon atom number of 3-8 or a
fluorine-substituted alkenoxy group having a carbon atom number of
3-8, wherein any one or more unconnected CH.sub.2 in the groups
represented by R.sub.3 and R.sub.4 may be substituted with
cyclopentyl, cyclobutyl or cyclopropyl;
[0018] Z.sub.1 and Z.sub.2 each independently represent a single
bond, --CH.sub.2CH.sub.2-- or --CH.sub.2O--;
##STR00006##
each independently represent
##STR00007##
##STR00008##
each independently represent one or more of
##STR00009##
[0019] m represents 1 or 2; and
[0020] p represents 0, 1 or 2.
[0021] Further preferably, in the liquid crystal composition
provided by the present invention, the total mass content of the
polymerizable liquid crystal composition is 0.001%-1%, the total
mass content of said one or more compounds of formula IV is
20%-80%, and the total mass content of said one or more compounds
of formula V is 20%-60%.
[0022] The compound represented by formula I is preferably from
compounds represented by formulas I-1 to 1-20, and the compound
represented by formula II is preferably from compounds represented
by formula II-1 to 11-15:
##STR00010## ##STR00011## ##STR00012## ##STR00013## ##STR00014##
##STR00015##
[0023] wherein
[0024] each S independently represents H, a C1-C5 alkyl group, a
C1-C5 alkoxy group, a fluorine-substituted C1-C5 alkyl group, a
fluorine-substituted C1-C5 alkoxy group, F or Cl, wherein any one
or more unconnected CH.sub.2 in the groups represented by S may be
independently replaced by --O--, --S--, --CO--, --CH.sub.2O--,
--OCH.sub.2--, --COO--, --OOC-- or an acrylate group or a
methacrylate group;
[0025] each P independently represents
##STR00016##
[0026] each Sp independently represents a single bond, a C1-C5
alkyl group, a C2-C5 alkenyl group, wherein any one or more
unconnected CH.sub.2 may be replaced by --O--, --S--, --CO--,
--CH.sub.2O--, --OCH.sub.2--, --COO--, --OOC-- or an acrylate
group; and
[0027] each o independently represents 0, 1, 2 or 3.
[0028] The compound represented by formula I is further preferably
from compounds represented by formulas I-1-1 to I-20-19, and the
compound represented by formula II is further preferably from
compounds represented by formulas II-1-1 to II-15-13:
##STR00017## ##STR00018## ##STR00019## ##STR00020## ##STR00021##
##STR00022## ##STR00023## ##STR00024## ##STR00025## ##STR00026##
##STR00027## ##STR00028## ##STR00029## ##STR00030## ##STR00031##
##STR00032## ##STR00033## ##STR00034## ##STR00035## ##STR00036##
##STR00037## ##STR00038## ##STR00039## ##STR00040## ##STR00041##
##STR00042## ##STR00043## ##STR00044## ##STR00045## ##STR00046##
##STR00047## ##STR00048## ##STR00049## ##STR00050##
##STR00051## ##STR00052## ##STR00053## ##STR00054## ##STR00055##
##STR00056## ##STR00057## ##STR00058## ##STR00059## ##STR00060##
##STR00061## ##STR00062## ##STR00063## ##STR00064## ##STR00065##
##STR00066## ##STR00067## ##STR00068## ##STR00069## ##STR00070##
##STR00071## ##STR00072## ##STR00073## ##STR00074## ##STR00075##
##STR00076## ##STR00077## ##STR00078## ##STR00079## ##STR00080##
##STR00081## ##STR00082## ##STR00083## ##STR00084## ##STR00085##
##STR00086## ##STR00087## ##STR00088## ##STR00089## ##STR00090##
##STR00091## ##STR00092## ##STR00093## ##STR00094##
##STR00095##
[0029] The compound represented by formula IV is preferably from
compounds represented by formulas IV-1 to IV-15; and the compound
represented by formula V is preferably from compounds represented
by formulas V-1 to V-12:
##STR00096## ##STR00097## ##STR00098##
[0030] wherein
[0031] R.sub.3 and R.sub.4 each independently represent an alkyl
group having a carbon atom number of 1-10, a fluorine-substituted
alkyl group having a carbon atom number of 1-10, an alkoxy group
having a carbon atom number of 1-10, a fluorine-substituted alkoxy
group having a carbon atom number of 1-10, an alkenyl group having
a carbon atom number of 2-10, a fluorine-substituted alkenyl group
having a carbon atom number of 2-10, an alkenoxy group having a
carbon atom number of 3-8 or a fluorine-substituted alkenoxy group
having a carbon atom number of 3-8, wherein any one or more
unconnected CH.sub.2 in the groups represented by R.sub.3 and
R.sub.4 may be substituted with cyclopentyl, cyclobutyl or
cyclopropyl.
[0032] For displays using these liquid crystal compositions, after
a polymerizable liquid crystal compound is added to an LC medium
and the LC medium is introduced into an LC cell, pre-tilting of
liquid crystal molecules can be formed by means of UV
photopolymerization or crosslinking under the application of a
voltage between electrodes. This is advantageous for simplifying
the LCD manufacturing process, increasing the response speed, and
reducing the threshold voltage.
[0033] The polymerizable liquid crystal compound provided by the
present invention has the advantages of an adjustable rate of
polymerization, a good mutual solubility with other monomers, a
good ultraviolet resistance, etc. As a reactive mesogen (RM), it
has the advantages of a good intermiscibility, a high charge
holding ratio (VHR), a high polymerization activity (less monomer
residue), etc., and is very suitable for use as an RM for PSA
(polymer supported alignment) and PS (polymer stabilized) mode
liquid crystal mixtures, especially in the case of PSA-VA and
PSA-IPS.
[0034] The amount (in mass percentage) of the polymerizable liquid
crystal composition added to the PSA-VA liquid crystal composition
is preferably between 0.01% and 1%, further preferably between
0.03% and 0.5%.
[0035] The amount (in mass percentage) of the polymerizable liquid
crystal composition added to the PSA-IPS liquid crystal composition
is preferably between 0.001% and 1%, further preferably between
0.005% and 0.1%.
[0036] The amount (in mass percentage) of the compound represented
by formula IV added to the liquid crystal composition is preferably
between 20% and 80%, further preferably between 20% and 40%.
[0037] The amount (in mass percentage) of the compound represented
by formula V added to the liquid crystal composition is preferably
between 20% and 60%, further preferably between 30% and 50%.
[0038] Said liquid crystal composition may be a negative liquid
crystal composition, and may further comprise one or more compounds
represented by formula VI:
##STR00099##
[0039] wherein
[0040] R.sub.5 and R.sub.6 each independently represent an alkyl
group having a carbon atom number of 1-10, a fluorine-substituted
alkyl group having a carbon atom number of 1-10, an alkoxy group
having a carbon atom number of 1-10, a fluorine-substituted alkoxy
group having a carbon atom number of 1-10, an alkenyl group having
a carbon atom number of 2-10, a fluorine-substituted alkenyl group
having a carbon atom number of 2-10, an alkenoxy group having a
carbon atom number of 3-8 or a fluorine-substituted alkenoxy group
having a carbon atom number of 3-8, wherein any one or more
CH.sub.2 in the groups represented by R.sub.5 and R.sub.6 may be
replaced by cyclopentyl, cyclobutyl or cyclopropyl; and
[0041] W represents O, S or --CH.sub.2O--.
[0042] Said liquid crystal composition may further comprise one or
more compounds represented by formula VII
##STR00100##
[0043] wherein
[0044] R.sub.7 and R.sub.8 each independently represent an alkyl
group having a carbon atom number of 1-10, a fluorine-substituted
alkyl group having a carbon atom number of 1-10, an alkoxy group
having a carbon atom number of 1-10, a fluorine-substituted alkoxy
group having a carbon atom number of 1-10, an alkenyl group having
a carbon atom number of 2-10, a fluorine-substituted alkenyl group
having a carbon atom number of 2-10, an alkenoxy group having a
carbon atom number of 3-8 or an fluorine-substituted alkenoxy group
having a carbon atom number of 3-8; and
##STR00101##
each independently represent 1,4-phenylene, 1,4-cyclohexylene or
1,4-cyclohexenylene.
[0045] The compound represented by formula VII is preferably:
##STR00102##
[0046] wherein R.sub.71 and R.sub.81 each independently represent
an alkyl group having a carbon atom number of 2-6 or an alkenyl
group having an atom number of 2-6;
[0047] R.sub.82 represents an alkoxy group having a carbon atom
number of 1-5; and
[0048] R.sub.71 and R.sub.81 are more preferably vinyl, 2-propenyl
or 3-pentenyl.
[0049] To the liquid crystal compounds provided by the present
invention, at least one functional additive may be further added,
and such functional additives mainly include antioxidants and
ultraviolet absorbers, selected from functional additives of
formulas VII and IX:
##STR00103##
[0050] wherein
[0051] R.sub.9 represents an alkyl group having a carbon atom
number of 1-10 or an alkoxy group having a carbon atom number of
1-10, and one or more methylene groups in the group represented by
R.sub.9 may be substituted with 1,4-cyclohexylene, 2,4-dioxane,
cyclopentyl and/or cyclopropyl;
[0052] each Y independently represents H or methyl; and
[0053] X represents 8, 10 or 12.
[0054] The present invention further relates to a liquid crystal
display element or liquid crystal display comprising any liquid
crystal composition as mentioned above; and said display element or
display is an active matrix display element or display or a passive
matrix display element or display.
[0055] Said liquid crystal display element or liquid crystal
display is preferably an active matrix addressing liquid crystal
display element or liquid crystal display.
[0056] Said active matrix display element or display is
specifically a PSVA-TFT or IPS-TFT liquid crystal display element
or display.
DETAILED DESCRIPTION OF EMBODIMENTS
[0057] The present invention is further described in conjunction
with particular examples below, but is not limited to the following
examples. Said methods are all conventional methods, unless
otherwise specified. Said raw materials are all commercially
available, unless otherwise specified.
[0058] In the present specification, the percentages are mass
percentages, the temperatures are in degree Celsius (.degree. C.),
and the specific meanings of other symbols and the test conditions
are as follows:
[0059] Cp represents the clearing point (.degree. C.) of a liquid
crystal as measured by means of a DSC quantitative method;
[0060] S--N represents the melting point (.degree. C.) for the
transformation of a liquid crystal from a crystal state to a
nematic phase;
[0061] .DELTA.n represents optical anisotropy, n.sub.o is the
refractive index of an ordinary light, n.sub.c is the refractive
index of an extraordinary light, with the test conditions being:
25.+-.2.degree. C., 589 nm and using an abbe refractometer for
testing;
[0062] .DELTA..di-elect cons. represents dielectric anisotropy,
with .DELTA..di-elect cons.=.di-elect cons..sub.//-.di-elect
cons..sub..perp., in which .di-elect cons..sub.// is a dielectric
constant parallel to a molecular axis, and .di-elect
cons..sub..perp. is a dielectric constant perpendicular to the
molecular axis, with the test conditions being 25.+-.0.5.degree.
C., a 20 micron parallel cell, and INSTEC: ALCT-IR1 for
testing;
[0063] .gamma.1 represents a rotary viscosity (mPas), with the test
conditions being 25.+-.0.5.degree. C., a 20 micron parallel cell,
and INSTEC: ALCT-IR1 for testing; and
[0064] .rho. represents electrical resistivity (.OMEGA.cm), with
the test conditions being: 25.+-.2.degree. C., and the test
instruments being a TOYO SR6517 high resistance instrument and an
LE-21 liquid electrode.
[0065] VHR represents a voltage holding ratio (%), with the test
conditions being: 20.+-.2.degree. C., a voltage of .+-.5 V, a pulse
width of 10 ms, and a voltage holding time of 16.7 ms. The test
equipment is a TOYO Model 6254 liquid crystal performance
comprehensive tester.
[0066] .tau. represents response time (ms), with the test
instrument being DMS-501 and the test conditions being:
25.+-.0.5.degree. C., a test cell that is a 3.3 micron IPS test
cell, an electrode spacing and an electrode width, both of which
are 10 microns, and an included angle between the frictional
direction and the electrode of 10.degree..
[0067] T (%) represents transmittance, with T (%)=100%*bright state
(Vop) luminance/light source luminance, with the test instrument
being DMS501, and the test conditions being: 25.+-.0.5.degree. C.,
a test cell that is a 3.3 micron IPS test cell, an electrode
spacing and an electrode width, both of which are 10 microns, and
an included angle between the frictional direction and the
electrode of 10.degree..
[0068] The conditions for the ultraviolet photopolymerization of a
polymerizable compound involve using ultraviolet light with a
wavelength of 313 nm and an irradiation light intensity of 0.5
Mw/cm.sup.2
[0069] In the examples of the invention of the present application,
liquid crystal monomer structures are represented by codes, and the
codes for ring structures, end groups and linking groups of liquid
crystals are represented as in Tables (I) and (II) below
TABLE-US-00001 TABLE (I) Codes corresponding to ring structures
Ring structure Corresponding code ##STR00104## C ##STR00105## P
##STR00106## G ##STR00107## Gi ##STR00108## Y ##STR00109## Sa
##STR00110## Sb ##STR00111## Sc
TABLE-US-00002 TABLE (II) Codes corresponding to end groups and
linking groups End group and linking group Corresponding code
C.sub.nH.sub.2n+1-- n- C.sub.nH.sub.2n+1O-- nO-- --OCF.sub.3 --OT
--CF.sub.2O-- --Q-- --CH.sub.2O-- --O-- --F --F --CN --CN
--CH.sub.2CH.sub.2-- --E-- --CH.dbd.CH-- --V-- --C.ident.C-- --W--
--COO-- --COO-- --CH.dbd.CH--C.sub.nH.sub.2n+1 Vn-- ##STR00112##
C(5)-- ##STR00113## C(3)--
EXAMPLES
##STR00114## ##STR00115##
TABLE-US-00003 [0070] Test parent 1: Category Liquid crystal
monomer code Content (%) V CY-C(5)-O4 11 V PY-C(5)-O2 9 V COY-3-O2
12 V CCOY-3-O2 8 V CY-5-O2 10 IV CC-3-V-1 5 IV CC-3-2 22 IV CC-2-5
8 IV CC-3-4 10 VII CCP-3-O1 5
TABLE-US-00004 Test parent 2: Category Liquid crystal monomer code
Content (%) V CY-3-O2 11 V PY-3-O2 9 V COY-3-O1 12 V CCOY-3-O2 8 IV
PP-5-1 10 IV CC-3-2 20 IV CC-3-5 5 VI Sa-C(5)1O-O2 5 VII CCP-3-1 10
VII CPP-3-2 10
TABLE-US-00005 Test parent 3: Category Liquid crystal monomer code
Content (%) V CCY-3-O2 11 V CPY-C(3)-O2 9 V CCY-2-O2 12 VI Sa-C(3)
1O-O4 8 IV PP-1-5 10 IV CC-3-2 24 IV CP-3-O2 11 IV CCP-3-1 10 VII
CPP-3-O2 5
TABLE-US-00006 Test parent 4: Category Liquid crystal monomer code
Content (%) V CCY-3-O2 11 V PY-3-O2 9 V CPY-3-O2 12 V CCOY-3-O2 8 V
CY-3-O4 12 IV CC-3-2 22 IV CC-3-5 10 IV CC-3-4 8 IV PP-5-O2 5 VII
CCP-3-O1 3
[0071] Experiment 1. Investigation of Solubility of Polymerizable
Liquid Crystal Compositions
[0072] Determination of low-temperature reliability of
polymerizable liquid crystal compositions added to different liquid
crystal parents
[0073] 1% of single component polymerizable compound RM1-5 is added
to test parents 1-4, respectively; and for comparison, a
polymerizable liquid crystal composition is added in equal quantity
to test parents 1-4, respectively, and the storage performance
thereof at -30.degree. C. in sample bottles are investigated.
TABLE-US-00007 Experiment -30.degree. C. number Sample composition
(5 d) Comparative Parent 1 RM-1 (1%) NG Example 1-1 Comparative
RM-3 (1%) NG Example 1-2 Comparative RM-5 (1%) NG Example 1-3
Example 1-1 RM-1 (0.5%) + RM-5 (0.1%) OK Example 1-2 RM-3 (0.5%) +
RM-5 (0.5%) OK Comparative Parent 2 RM-2 (1%) NG Example 1-4
Comparative RM-4 (1%) NG Example 1-5 Comparative RM-5 (1%) NG
Example 1-6 Example 1-3 RM-2 (0.5%) + RM-5 (0.1%) OK Example 1-4
RM-4 (0.5%) + RM-5 (0.5%) OK Comparative Parent 3 RM-1 (1%) NG
Example 1-7 Comparative RM-3 (1%) NG Example 1-8 Comparative RM-5
(1%) NG Example 1-9 Example 1-5 RM-1 (0.5%) + RM-5 (0.5%) OK
Example 1-6 RM-3 (0.5%) + RM-5 (0.5%) OK Example 1-7 RM-1 (0.4%) +
RM-3 (0.4%) + OK RM-5 (0.2%) Comparative Parent 4 RM-2 (1%) NG
Example 1-10 Comparative RM-2 (1%) NG Example 1-11 Comparative RM-4
(1%) NG Example 1-12 Comparative RM-5 (1%) NG Example 1-13 Example
1-8 RM-2 (0.5%) + RM-5 (0.5%) OK Example 1-9 RM-3 (0.5%) + RM-5
(0.5%) OK Example 1-10 RM-4 (0.5%) + RM-5 (0.5%) OK
[0074] As can be seen from the above table, comparing Comparative
Examples 1-1 to 1-13 with Examples 1-1 to 1-10, none of the
low-temperature reliabilities of the compositions in which the
monomer of formula I or the monomer of formula II is used alone can
achieve criteria, whereas the low-temperature reliabilities of the
compositions in which the monomer of formula II and the monomer of
formula I are used can achieve the criteria.
[0075] The non-benzene ring structures in formula I and formula II
can increase the solubilities of the polymerizable monomers. It is
an essential component in the polymerizable liquid crystal
composition.
[0076] Experiment 2. Evaluation of Conversion Rate of Polymerizable
Liquid Crystal Compositions
[0077] Determination of rate of polymerization of polymerizable
liquid crystal compositions added to different liquid crystal
parents
[0078] 4000 ppm of single component polymerizable compound RM1-6 is
added to test parents 1-4, respectively; and for comparison, a
polymerizable liquid crystal composition is added in equal quantity
to test parents 1-4, respectively; liquid crystal media are
prepared by the liquid crystal medium preparation method mentioned
above, the liquid crystal media are filled into liquid crystal
cells, a PSA panel process 1 is simulated, and the rates of
polymerization thereof are determined, with the specific conditions
being: UV1: 72 mW/cm.sup.2@365 nm, 100 s; furthermore, the liquid
crystal cells are cut open for HPLC analysis, and the results of
the rate of polymerization under UV1 conditions are compared and as
shown in the following table.
TABLE-US-00008 UV1 Experiment conversion number Sample composition
rate (%) Comparative Parent 1 RM-1 (0.4%) 87 Example 2-1
Comparative RM-3 (0.4%) 55 Example 2-2 Comparative RM-5 (0.4%) 31
Example 2-3 Example 2-1 RM-1 (0.3%) + RM-5 (0.1%) 80 Example 2-2
RM-3 (0.3%) + RM-1 (0.1%) 49 Comparative Parent 2 RM-2 (0.4%) 85
Example 2-4 Comparative RM-4 (0.4%) 64 Example 2-5 Comparative RM-5
(0.4%) 33 Example 2-6 Example 2-3 RM-2 (0.2%) + RM-5 (0.2%) 62
Example 2-4 RM-4 (0.2%) + RM-5 (0.2%) 49 Comparative Parent 3 RM-1
(0.4%) 90 Example 2-7 Comparative RM-3 (0.4%) 59 Example 2-8
Comparative RM-5 (0.4%) 33 Example 2-9 Example 2-5 RM-1 (0.3%) +
RM-5 (0.1%) 78 Example 2-6 RM-3 (0.3%) + RM-1 (0.1%) 53 Example 2-7
RM-1 (0.2%) + RM-3 (0.1%) + 74 RM-5 (0.1%) Comparative Parent 4
RM-3 (0.4%) 62 Example 2-10 Comparative RM-4 (0.4%) 68 Example 2-11
Comparative RM-5 (0.4%) 35 Example 2-12 Example 2-8 RM-3 (0.36%) +
RM-5 (0.04%) 60 Example 2-9 RM-4 (0.36%) + RM-5 (0.04%) 66
[0079] As can be seen from the above table, comparing Comparative
Examples 2-1 to 2-12 with Examples 2-1 to 2-9, the rates of
polymerization of those having the same RM in different parents are
different, which is in line with general industry knowledge, and
also brings challenges in terms of the types and quantities of
polymers added to the LCDs to different LCD manufacturers when
carrying out liquid crystal formulation. Overall, the conversion
rate of the polymerizable compound of formula I is higher than that
of the polymerizable compound of formula II, and the conversion
rate of the polymerizable compound of formula I is too fast,
resulting in a risk of forming broken bright spots, so that it is
not suitable for use alone. By means of the polymerizable
composition provided by the present invention formed by the
adjustment of the polymerizable compounds of formula I and formula
II, the effects of different rates of polymerization can be
achieved.
[0080] Furthermore, it can be found that after the polymerization
and mixing of different components, the rate of polymerization
thereof does not lie in a simple weighted average relationship,
wherein among the components, some tend towards the fast components
after being promoted by each other, some have no effect, some tend
towards the slow components, and some may tend to be slower than
the slowest component due to being diluted with each other;
therefore, it is very important to carry out the adjustment of the
polymerizable liquid crystal composition.
[0081] Experiment 3. Evaluation of Reliability and Pretilt Angle of
Polymerizable Liquid Crystal Compositions
[0082] The same liquid crystal compositions as in Experiment 2 are
used, wherein the small number liquid crystal components in the
samples of Example 3 are the same as the small number liquid
crystal components in Example 2, e.g., the liquid crystal component
in Example 3-2 is equivalent to that in Example 2-2.
[0083] PSA panel process 2 is completed on the basis of Experiment
2, with the specific conditions being: UV2: 5 mW/cm.sup.2@365 nm,
and 100 min, and the final conversion rate, voltage holding ratio
(VHR), and pretilt angle thereof are tested, wherein due to the
PSVA mode, the pretilt angle is actually evaluated by using a
90-measured value during the evaluation.
TABLE-US-00009 UV1 UV2 Experiment conversion conversion Pretilt
angle number rate (%) rate (%) (.degree.) VHR Comparative 87 99
87.8 99.1 Example 3-1 Comparative 55 90 88.9 99.0 Example 3-2
Comparative 31 76 89.0 99.3 Example 3-3 Example 3-1 80 98 88.8 99.5
Example 3-2 49 87 88.9 99.7 Comparative 85 99 87.6 99.0 Example 3-4
Comparative 64 93 88.1 99.3 Example 3-5 Comparative 33 77 89.3 99.1
Example 3-6 Example 3-3 62 92 88.7 99.4 Example 3-4 49 87 88.3 99.5
Comparative 90 99 87.3 99.1 Example 3-7 Comparative 59 90 88.1 99.3
Example 3-8 Comparative 33 77 88.9 99.2 Example 3-9 Example 3-5 78
96 88.4 99.5 Example 3-6 53 88 88.6 99.6 Example 3-7 74 94 88.6
99.5 Comparative 62 97 87.8 99.1 Example 3-10 Comparative 68 94
87.9 99.4 Example 3-11 Comparative 35 76 88.3 99.2 Example 3-12
Example 3-8 60 97 88.6 99.5 Example 3-9 66 82 88.6 99.6
[0084] As can be seen from Comparative Examples 3-1 to 3-12 and
Examples 3-1 to 3-9, although the difference in conversion rate
after UV1 is relatively large, the difference in conversion rate
after UV2 is decreased; furthermore, the final pretilt angles of
samples with similar conversion rates are also different; the
conversion rates of some of the single component samples of formula
I are too fast, and uneven sample particles may cause the pretilt
angle thereof to be too large, thereby forming a large Bump, easily
causing light leakage; however, the mixed samples to which formula
II is added have a relatively stable pretilt angle, can suppress
the generation of larger particles, contributing to the stability
of the pretilt angle. Therefore, under the premise of satisfying
the processes of LCD manufacturers, the polymer particles are
uniform, and the pretilt angle is appropriate, which are the
characteristics of the adjustment of the polymerizable liquid
crystal mixture. The voltage holding ratio (VHR) data obtained by
the tested samples are all excellent, and the data of the examples
in which polymerizable liquid crystal compositions of components of
formula I and formula II are added to the same parent for
comparison (for different parents, direct comparison is impossible)
are significantly preferred.
[0085] Experiment 4. Evaluation of Reliability of Functional
Additives on Polymerizable Liquid Crystal Compositions
[0086] On the basis of Experiment 3, the same liquid crystal
compositions as those in Comparative Example 3-12, Example 3-5 and
Example 3-7 are selected for an aging test; polymerizable compounds
are polymerized by means of ultraviolet irradiation, and tested
under the conditions of ultraviolet light, a high temperature, etc.
for the voltage holding ratios (VHR) thereof; in addition, by
adding functional additives to Example 3-5 and Example 3-7, the
voltage holding ratios (VHR) of Examples 4-1 to 4-6 are further
investigated under the conditions of ultraviolet light, a high
temperature, etc.
TABLE-US-00010 VHR VHR (high Experiment VHR (ultra- temper- number
Composition (initial) violet) ature) Comparative Comparative 99.2
95.2 93.7 Example 4-1 Example 3-12 Comparative Example 3-5 99.5
97.2 97.1 Example 4-2 Example 4-1 Example 3-5 + 200 99.2 97.6 99.0
ppm of Additive-1 Example 4-2 Example 3-5 + 100 99.3 99.0 97.8 ppm
of Additive-2 Example 4-3 Example 3-5 + 100 99.1 98.5 98.7 ppm of
Additive-1 + 100 ppm of Additive-2 Comparative Example 3-7 99.5
97.4 97.6 Example 4-3 Example 4-4 Example 3-7 + 200 99.2 97.7 98.9
ppm of Additive-1 Example 4-5 Example 3-7 + 100 99.2 99.1 98.1 ppm
of Additive-2 Example 4-6 Example 3-7 + 200 99.1 98.7 99.0 ppm of
Additive-1 + 100 ppm of Additive-2
[0087] As can be seen from Comparative Examples 4-1 to 4-3, the VHR
after ultraviolet irradiation and the VHR after high temperature of
the samples are significantly reduced as compared with the initial
VHR thereof; and the reductions in the VHRs after ultraviolet
irradiation and high temperature of Comparative Example 4-2 and
Comparative Example 4-3 manufactured from Example 3-5 and Example
3-7 are smaller than those of Comparative Example 4-1, indicating
that the VHRs after ultraviolet irradiation and high temperature
thereof can be improved after being mixed with RM;
[0088] in addition, as can be seen from Examples 4-1 to 4-6, the
VHR after high temperature and the VHR after ultraviolet
irradiation are both improved after the addition of additive-1 and
additive-2 in the liquid crystal composition, and the effects of
improvement of additive-1 and additive-2 are not the same, wherein
additive-1 focuses on improving the VHR after high temperature, and
improves the VHR after ultraviolet irradiation, but the amplitude
of the improvement is not as good as the effect after high
temperature; and additive-2 focuses on improving the VHR after
ultraviolet irradiation, and improves the VHR after high
temperature, but the amplitude of the improvement is not as good as
the effect after ultraviolet irradiation; however, using additive-1
and additive-2 in combination can achieve more ideal results; of
course, the addition of the additives will cause the initial value
to decrease, and the addition amount and type thereof should be
used according to specific circumstances.
* * * * *